RU2470970C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition contains low-molecular hydroxyl-containing butadiene-isoprene rubber - a product of copolymerisation of low-molecular hydroxyl-containing butadiene-isoprene rubber PDI-1K with liquid products of pyrolysis of straight-run gasoline with boiling range of 130-190°C in weight ratio of 1:(0.3:1), obtained in a toluene solution in the presence of an initiator - α,α'-dioxybenzyl peroxide polyisocyanate, urethane-formation catalyst - tin dibutyl dilaurate, glycerine.

EFFECT: improved dynamic and physical properties of the coating.

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Description

The invention relates to rubber coatings based on liquid hydrocarbon rubbers intended for the device of coatings mainly for sports fields, floors, roofing and insulation coatings in construction.

A known composition for coatings, including copolymers of butadiene and piperylene with a molecular weight of 1200-3200 and 500-1200, glycerin, polyisocyanate, a urethane formation catalyst and rubber crumb (RF patent 1229214, MKI C09D 3/72, 1984). The disadvantage of the coating of this composition are low dynamic and elastic hysteresis properties.

Known composition for coatings, including low molecular weight butadiene-piperylene rubber with a molecular weight of 1200-3200, glycerin, polyisocyanate, a urethane formation catalyst, hydroxylated rubber crumb and calcium oxide (RF patent 2024564, IPC C09D 109/00, 1994).

The disadvantage of this composition is the low dynamic and elastic hysteresis properties due to the wide molecular weight distribution and low functionality of butadiene-piperylene rubber.

A known coating composition, including butadiene-piperylene rubber, glycerin, polyisocyanate, a urethane formation catalyst, calcium oxide, chalk, an antioxidant is a product of polymerization of isoprene production waste - decomposition stage 4.4 of dimethyldioxane-1,3 (RF patent 1775447, IPC С09D 109/00, 1990).

The disadvantage of this composition is the low dynamic and elastic hysteresis properties.

A known coating composition comprising a copolymer of butadiene with isoprene with a monomer ratio of 70:30, a molecular weight of 4000-5000, a hydroxyl content of 0.75-0.89 wt.%, A plasticizer, a mineral filler, a trifunctional low molecular weight alcohol, polyisocyanate, a urethane formation catalyst 2,4,6-tri-tert-butylphenol and ethyl silicate (RF patent 2186812, IPC С09D 109/00, 2000).

The coating of this composition has low dynamic and elastic hysteresis properties.

The closest solution to the proposed invention in technical essence is a coating composition (RF patent 2266935, IPC C09D 109/00, C09D 175/14, 12/27/2005), including low molecular weight rubber, polyisocyanate, a urethane formation catalyst as a low molecular weight rubber, contains a hydroxyl-containing isoprene copolymer with butadiene with a monomer ratio of 20:80, an average molecular weight of 3000-3500, a hydroxyl group content of 0.7-1.1 wt.% (PDI-1K), and the composition further comprises polycaproamide production waste, as follows component ratio, mass parts .:

Isoprene and Butadiene Copolymer (PDI-1K) one hundred Polyisocyanate 10-36 Polycaproamide Production Wastes 0.5-40 Urethane Catalyst 0.001-3.0

The composition further comprises moisture absorption components, a filler, a plasticizer, a solvent, a low molecular weight alcohol, an antioxidant, a pigment, a surfactant.

The coating of this composition has insufficient strength and deformation due to the low level of dynamic and elastic hysteresis properties. This is due to the defectiveness of the three-dimensional structure of the mesh formed during curing. Therefore, the polymer network formed during curing of the rubber has a significant number of defects in the form of free ends that do not absorb the load under impact. In addition, the weak adhesive interaction at the interface of the polymer-mineral filler does not allow to obtain coatings with the required strength.

The technical result is an increase in the dynamic and physico-mechanical properties of the coating.

The technical result is achieved in that the coating composition based on low molecular weight hydroxyl-containing butadiene-isoprene rubber, including polyisocyanate, the urethane formation catalyst - tin dibutyl dilaurate, glycerin, is characterized in that the copolymerization product of low molecular weight hydroxylated liquid products of pyrolysis of straight-run gasolines with boiling limits from 130-190 ° C at a mass ratio of 1: (0.3: 1) obtained in a solution of ol, in the presence of an initiator - α, α'-dioksibenzilperoksida, with the following component ratio, mass parts .:

Specified Modified Rubber one hundred Polyisocyanate 12-24 Tin Dibutyl Dilaurate 0.001-0.1 Glycerol 1-5

A method of obtaining a modified low molecular weight hydroxyl-containing butadiene-isoprene rubber is carried out in the following way: hydroxyl-containing low molecular weight butadiene rubber PDI-1K (a copolymer of isoprene with butadiene with a monomer ratio of 20:80, a molecular weight of 3000-3500, a hydroxyl content of 0.7-1.1 wt. %) is dissolved in aromatic hydrocarbon - toluene in the ratio of rubber: toluene 1: 1 and mixed with liquid pyrolysis products (GIP) in the ratio: 1: (0.33: 1), respectively. After the mixture of ZHP and a solution of hydroxyl-containing low molecular weight butadiene rubber in toluene is heated in a glycerin bath to 110-130 ° C for 1.5-2 hours. To isolate the modified low molecular weight hydroxyl-containing butadiene-isoprene rubber, unreacted hydrocarbons are distilled off under vacuum of 25-30 mm Hg. Art. at a temperature of 130 ° C. The composition of GSP of straight-run gasolines with boiling limits of 130-190 ° С is presented in Table 1 (Bondaletov O.V. Copolymerization of liquid pyrolysis products and acrylic monomers. / Bondaletov OV, L.I. Bondaletova, I.V. Tyumentseva, V. G. Bondaletov, V. M. Sutyagin. / Polzunovsky Bulletin 2009, No. 3, pp. 24-28].

Polymethylene - polyphenyl isocyanates based on 4,4'-diphenylmethanediisocyanate (TU-6-03-375-75, 113-03-38-106-90, 113-03-603-86, 2224-152- 04691277-96).

Tin dibutyl dilaurate (TU 6-02-818-73) is used as a catalyst for urethane formation.

Table 1 The composition of ZhPP straight-run gasolines with boiling limits of 130-190 ° C Components The composition of the ZhPP,% Cyclopentadiene 4.3 Benzene 3.0 Toluene 8.8 Ethylbenzene 5.7 Xylene 23.7 Styrene 16.6 Methyl ethyl benzene 6.8 α-methyl styrene 3.0 Dicyclopentadiene 20.1 Inden 3.2 Indena derivatives 2,3 Methyl cyclopentadiene dimer 1.7 Unidentified hydrocarbons 0.8 Including unsaturated hydrocarbons 51.2

An example of obtaining a modified low molecular weight hydroxyl-containing butadiene-isoprene rubber.

20 g of hydroxyl-containing low molecular weight butadiene-isoprene rubber are loaded into the reactor and dissolved in 20 g of toluene, a homogeneous mixture is obtained in which 20 g of fatty acids and 0.4 g of α, α'-dioxibenzyl peroxide (0.67% wt.) Are dosed. Heated in a glycerin bath to 110-130 ° C for 2 hours. Unreacted hydrocarbons and a toluene solvent are distilled off under a vacuum of 25-30 mm Hg. Art. The yield of the modified low molecular weight hydroxyl-containing butadiene-isoprene rubber is about 100%.

For the manufacture of the composition using mixing equipment, ensuring the homogenization of the polyisocyanate and the catalyst in rubber. The degree of milling of solid particles should not exceed 100 microns. In the industrial use of the composition, the polyisocyanate is supplied complete with the composition and introduced into it immediately before coating.

The invention is illustrated by the following example. 300 g of modified low molecular weight hydroxyl-containing butadiene-isoprene rubber, 72 g of polyisocyanate (4,4'-diphenylmethanediisocyanate), 0.3 g of urethane-forming catalyst (tin dibutyl dilaurate) are loaded into a mixer with a 1 liter volume mixer, 15 g of glycerol are mixed, mix for 10 minutes . The resulting mass is poured onto molds and kept at a temperature not lower than 20 ° C for 3-5 days. The composition corresponds to example 1 in table 2.

Other compositions of the prototype are similarly prepared, the compositions of which are shown in table 2.

Tests of the coating material are carried out in accordance with GOST 263-93, GOST 270-75.

The properties of the obtained coating samples are shown in table 3.

From the data of table 3 it is seen that the use of a modified low molecular weight hydroxyl-containing butadiene-isoprene rubber in combination with polyisocyanate, glycerin and a urethane formation catalyst (tin dibutyl dilaurate) provides a coating with higher strength and deformation than that of the prototype. Coatings from compositions 6-7 have the worst properties, which is associated with a deviation of the content of the components of the composition from the optimal.

table 2 Name of components Composition, parts by weight Prototype Pat. RF 2266935 one 2 3 four 5 6 7 1. Low molecular weight hydroxyl-containing butadiene-isoprene rubber: PDI-1K one hundred 2. Modified low molecular weight hydroxyl-containing butadiene-isoprene rubber PDI-1K (with a mass ratio of rubber - liquid pyrolysis products) 100 (1: 0.1) 100 (1: 0.3) 100 (1: 0.6) 100 (1: 0.6) 100 (1: 1) 100 (1: 1.5) 100 (1: 2) - 3. Low molecular weight alcohol: glycerin 5 four 3 one four 0.8 7 one 4. Polyisocyanate: 4.4'-diphenylmethanediisocyanate 24 22 19 12 twenty 8 25 twenty 5. Urethane Catalyst: Tin Dibutyl Dilaurate 0.1 0.01 0.1 0.01 0.01 0.2 0.0001 0.5 6. Waste from polycaproamide production 35

The use of low molecular weight hydroxyl-containing butadiene-isoprene rubber with mass. the ratio of rubber - liquid pyrolysis products of more than 1: 1 in the composition leads to a sharp decrease in physical and mechanical properties, less than 1: 0.3 - does not affect the properties of the composition.

The introduction of the urethane catalyst less than 0.001 wt.h. impractical due to the long curing time of the coating composition. An increase of more than 0.1 parts by weight reduces the pot life of the composition.

The decrease in the number of polyisocyanate less than 12 wt.h. leads to the formation of a weakly crosslinked structure and the formation of a gel-like product. An increase of over 24 parts by weight impractical due to the tendency to foaming during curing.

Table 3 The name of indicators The properties Prototype Pat. RF 2266935 one 2 3 four 5 6 7 1. Shore A hardness, cu 58 70 72 70 72 56 53 56 2. Conditional strength, kg / cm ² 13 twenty 25 27 twenty fourteen 10 12 3. Elongation at break,% 75 150 168 180 182 55 70 60 4. The rebound elasticity,% 40 42 55 53 45 42 33 42

Thus, the claimed composition for coatings has enhanced dynamic and physico-mechanical properties.

Claims (1)

Composition for coatings based on low molecular weight hydroxyl-containing rubber, including polyisocyanate, a urethane-forming catalyst - tin dibutyl dilaurate, glycerin, characterized in that the rubber is a copolymerization product of low molecular weight hydroxyl-containing butadiene rubber with the use of 130 -190 ° C with a mass ratio of 1: (0.3: 1) obtained in a toluene solution in the presence of an initiator, α, α'-dioxibenzyl peroxide, at eduyuschem component ratio, mass parts .:
Specified Modified Rubber one hundred Polyisocyanate 12-24 Tin Dibutyl Dilaurate 0.001-0.1 Glycerol 1-5